Effect of defect energy on strain-gradient predictions of confined single-crystal plasticity

Gurtin recently proposed a strain-gradient theory for crystal plasticity in which the gradient effect originates from a defect energy that characterizes energy storage due to the presence of a net Burgers vector. Here we consider a number of different possibilities for this energy: specifically, working within a simple two-dimensional framework, we compare predictions of the theory with results of discrete-dislocation simulations of stress relaxation in thin films. Our objective is to investigate which specific defect energies are capable of capturing the size-dependent response of such systems for different crystal orientations.     

Dependence of nonlinear elasticity on filler size in composite polymer systems

Nanosized filler particles enhance the mechanical properties of polymer composites in a size-dependent fashion. This is puzzling, because classical elasticity is inherently scale-free, and models for the elasticity of composite systems never predict a filler-size dependence. Here, we study the industrially important system of silica-filled rubbers, together with a well-characterized model-filled crosslinked gel and show that at high filler content both the linear and nonlinear elastic properties of these systems exhibit a unique scaling proportional to the cube of the volume fraction divided by the particle size. This remarkable behavior makes it possible to predict the full mechanical response of particle-filled rubbers for small but finite deformations based solely on the rheology of the matrix and the size and modulus of the filler particles.     

Gas-phase halonium metathesis and its competitors. Skeletal rearrangements of cationic adducts of saturated ketones

The methyl cation and CF(3)(+) attack saturated, acyclic ketones to make vibrationally excited adduct ions. Despite their high internal energies and short lifetimes, these adducts undergo deep-seated rearrangements that parallel slower processes in solution. Observed pathways include alkene and alkane expulsions, in addition to (in the case of CF(3)(+)) the precedented loss of CF(2)O + HF. For the vast majority of ketones, the principal charged products are the CF(3)(+) adducts of lighter carbonyl compounds, ions that are not easily prepared by other avenues. Evidence for ion structures comes from collisionally activated unimolecular decomposition and bimolecular ion-molecule reactions. Typical examples are di-n-propyl and diisopropyl ketones (both of which produce CH(3)CH=OCF(3)(+) as the principal ion-molecule reaction product) and pentamethylacetone (which produces (CH(3))(2)C=OCF(3)(+) as virtually the sole ion-molecule reaction product). Isotopic labeling experiments account for mechanisms, and DFT calculations provide a qualitative explanation for the relative abundances of products from unimolecular decompositions of the chemically activated CF(3)(+) adduct ions that are initially formed.     

Taxol® (Paclitaxel)

Taxol® (paclitaxel) has been hailed by many as the most promising new cancer treatment in two decades. The FDA requires that paclitaxel intended for human consumption be obtained only from the bark ofTaxus brevifolia, the Pacific yew. As this may become increasingly uneconomical, new strategies must be explored to ensure the continued availability of taxol and related molecules. This article examines the planning that must be engaged in and the contingencies that must be prepared for in this changing arena.     

Thermodynamics and the cohesive zone in fracture

This paper discusses the thermodynamics of the cohesive zone preceding a running crack. Appropriate forms of the first two laws are given and some simple constitutive equations are discussed.

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Zusammenfassung In dieser Arbeit wird die Thermodynamik der Kohäsions-Zone diskutiert, die einem laufenden Riss voraneilt. Es werden passende Formen der ersten zwei Hauptsähe angegeben, und es werden einige einfache Stoffgleichungen diskutiert.